Substituted guanidines



Patented; Mar. 22, 1932 UNITED STATES PATENT OFFICE}.

HELMUTH :MEIS, OF WIESDOIRF, GERMANY, ASSIGNOB TO I. G. FARBENINDUSTBIE.

AKTIENGESELLSOHAFT, F"FRANKFORT-ON-THE-MAIN, GERMANY, A CORPORATION OF GERMANY SUBSTITUTED GUANIIDINES I No Drawing. Application filed August 20, 1928 Serial No.1300,965, and in Germany January 10, 1927. v

The present invention'relates to a process for the production of substituted guanidines and to new compoundsobtainable thereby, more particularly toa process of preparing guanidines of the probable general formula NHIR N x. wherein R meansan aliphatic-, aromatic ali:

phatic-aromatic or hydroaromatic hydrocar-- bon radicle, X stands for the residue of a secondary aliphatic amine.

The process of their production consists 1n reacting upon a substituted thiourea of the general formula Nan wherein R represents an aliphatic-, aromatio, aliphatic-aromatic or hydroaromatic hydrocarbon radicle with a secondary aliphatic amine, which latter term is intended to include heterocyclic compounds containing an NH group as part of a "fully hydrogenated six membered ring, such as piperidine, hexahydroquinoline and the like. is performed in the presence of an organic or inorganic desulfurizing zinc compound and a compound of the group comprising the oxides and hydroxides of the alkalies and alkaline earth metals. Probably the mechanism of the reaction will be for instance as follows NH-R H s /N-Rd 1k 1 /NH-R 1 8.1111118 04S nag: ilmofl a Y \NH-R \N-R alkyl When working with PTPGIldlIle a compound of the probable formula /NH- R O=N-R c i \N/CH2 on 2r CHrC/Bh will be formed in the same manner, and similar products are obtainable when replacing .59 the piperidine by one of its homologues,

The reaction whereby it is to bevunderstood, that ringhomologues of piperidine, such as hexahydroqulnoline andthe like areintendedto'be included in the invention.

The products thus obtainable are bases forming salts with mineral acids and dithiocarbamates when treated with one mol of carbon disulfide and one mol' of a secondary aliphatic amine according to the equation The new products are intended to be used as.

'lVhen cooled the reaction mass is filtered and from the residue the diphenyl dimethylguanidine of the probable formula H= N CH3 solvent such as alcohol, benzene, toluene, diluted acetic acid etc. When working with the latter solvent the guanidine derivative may be precipitated with soda lye. It forms an oily substance and may be used in this state of purity as an accelerator in vulcanization processes. When dissolving the oily substances in alcohol or diluted acetic acid and adding'nitric acid or an alkali metal following examples will illustrate my nitrate, a difficultly soluble. compound isprecipitated, which melts at199 C. and is probably the nitrate of the diphelllyldimethylguanidine.

Example 2.-50 kg. of thiocarbanilide are 35 is extracted by means of a suitable organic stirred with 65 kg. of zinc sulfate, 100 liters of concentrated soda lye (about 30% strength) and 100 kg. of piperidine in 400 liters of water at a temperature of about 60 C. until no organically bound sulfur can any more be detected. Now the excess of piperidine is removed by steam distillation and the diphenylpiperidylguanidine of the probable formula is isolatedby extraction with diluted acetic acid. It forms an oily substance which on treatment with hydrochloric acid yields a solid chlorohydrate difficultly soluble in cold water.

This is a continuation in part of my copending application Ser. Not 214,784, filed wherein R represents an aliphatic-, aromatic-, aliphatic-aromatic or hydroaromatic hydrocarbon radicle with a secondary aliphatic amine in the presence of a desulfurizing zinc compound and a compound of the group consisting of the oxides and hydroxides of the alkalies and alkaline earth metals.

I 2. The process which comprises reacting upon thiocarbanilide with a secondary aliphatic amine in the presence of a desulfurizing zinc compound and a compound of the group consisting of the oxides and hydroxides of the alkalies and alkaline earth metals.

3. The process which comprises reacting upon thiocarbanilide with dimethylamine in the presence of zinc hydroxide and soda lye.

4. The new compounds of the probable formula wherein X stands for the residue of a secondary aliphatic amine and R represents an 5. The new compounds of the probable formula CH: N CHI said compound being an oily substance, formin a nitrate of the melting point 199 C.

n testimony whereof I have hereunto set my hand.

HELMUTH MEIS. '[L. s.] 

